TW201117389A - A paste composition for making electrode of solar-cell - Google Patents

A paste composition for making electrode of solar-cell Download PDF

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TW201117389A
TW201117389A TW099124714A TW99124714A TW201117389A TW 201117389 A TW201117389 A TW 201117389A TW 099124714 A TW099124714 A TW 099124714A TW 99124714 A TW99124714 A TW 99124714A TW 201117389 A TW201117389 A TW 201117389A
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Taiwan
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electrode
solar cell
poly
paste
forming
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TW099124714A
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Chinese (zh)
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Kun-Ho Hwang
Yong-Jun Jung
Min-Soo Ko
Mee-Hye Jeong
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Dongjin Semichem Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/0745—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

The present invention relates to a paste for forming an electrode of a solar cell. The paste for forming an electrode of a solar cell according to the present invention has high electrical conductivity, low contact resistance, high aspect ratio, superior storage stability, and superior adhesion properties. The paste of the present invention is solidified at a drying temperature and is thus formed into an electrode without a separate firing process during the formation of the electrode of the solar cell, thereby improving productivity in forming the electrode of the solar cell.

Description

201117389 六、發明說明： 【發明戶斤屬之技術領域3 發明領域 本發明係有關於一種太陽電池之電極形成用糊，依據 本發明獲得之太陽電池之電極形成用糊顯示低接觸電阻、 高縱橫比、優異的貯藏安定性以及優異的接著力，由於在 太陽電池之電極形成時不經歷額外的燒成步驟，且在乾燥 溫度施行硬化形成電極，所以太陽電池之電極形成的生產 性南。 【先前技術3 發明背景 習知在太陽電池之電極形成時由於燒成溫度係350°C 以上的高溫，所以糊内的有機物容易除去。但是，當要求 燒成溫度在350°C以下之電極材料之情形，因糊内的有機物 殘存而發揮電化學絕緣體之作用，會阻礙電子流動。特別 是太陽電池領域之中在非晶質/晶質矽異質接面太陽電池 之情形，因非晶質層的結晶化抑制而要求低溫(250°C以下) 之燒成條件。這種低溫燒成用電極中因殘存有機物會產生 電特性降低的問題。 【發明内容】 發明概要 發明欲解決之課題 從而，本發明之目的在於提供一種太陽電池之電極形 成用糊以及利用其之太陽電池之電極形成方法，該太陽電 201117389 池之電極形成用糊顯示低接觸電阻、高縱橫比、優異的貯 藏安定性以及優異的接著力，由於在太陽電池之電極形成 時不經歷額外的燒成步驟，且在乾燥溫度施行硬化形成電 極’所以可以提高太陽電池之電極形成的生產性。 用以欲解決課題之手段 為達成前述目的，本發明提供一種太陽電池之電極形 成用糊，其包含 (a) 銀粉末(silver powder); (b) 導電性高分子，係由PEDOT-PSS、聚噻吩 (Polythiophene)、聚(3-烷基噻吩)(p〇ly(3-alkylthiophene))、 聚吡咯(Polypyrrole)、聚((2,5二烷氧基)-p-伸苯基伸乙烯基） (Poly((2,5dialkoxy)-p-phenylene vinylene))、聚(p-伸苯基伸 乙烯基）(P〇ly(p-phenylene vinylene))以及聚（p-伸苯基） (Poly(p-phenylene))組成之族群中選出的1種以上者； (c) 纖維素衍生物；以及 (d) 溶劑。 另外’本發明提供一種利用前述太陽電池之電極形成 用糊的太陽電池之電極形成方法，利用前述方法形成之太 陽電池電極’以及包含前述電極之太陽電池。 發明效果 依據本發明獲得之太陽電池之電極形成用糊顯示如下 所述之效果： 第一，高生產性：由於在乾燥溫度（1〇〇〜250。(：以下） 下短時間硬化的同時形成電極，所以不需要額外的燒成步 201117389BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paste for forming an electrode for a solar cell, and the paste for electrode formation of a solar cell obtained according to the present invention exhibits low contact resistance and high aspect. The production stability of the electrode of the solar cell is south because the ratio of the storage stability and the excellent adhesion are excellent, since the electrode is not subjected to an additional baking step when the electrode of the solar cell is formed, and the electrode is formed by hardening at the drying temperature. [Prior Art 3] It is known that when the electrode of the solar cell is formed, the firing temperature is a high temperature of 350 ° C or higher, so that the organic matter in the paste is easily removed. However, when an electrode material having a firing temperature of 350 ° C or lower is required, the organic substance in the paste remains as an electrochemical insulator, which hinders the flow of electrons. In particular, in the case of a solar cell in the field of solar cells, in the case of amorphous/crystalline germanium heterojunction solar cells, low temperature (250 ° C or lower) firing conditions are required due to suppression of crystallization of the amorphous layer. In such an electrode for low-temperature firing, there is a problem that electrical properties are lowered due to the residual organic matter. SUMMARY OF THE INVENTION The object of the present invention is to provide a paste for forming an electrode for a solar cell and a method for forming an electrode for a solar cell using the same, wherein the electrode for forming an electrode of the solar cell 201117389 shows low contact Resistance, high aspect ratio, excellent storage stability, and excellent adhesion, since the electrode of the solar cell is not subjected to an additional firing step and is hardened at a drying temperature to form an electrode, the electrode formation of the solar cell can be improved. Productive. Means for Solving the Problems In order to achieve the above object, the present invention provides a paste for forming an electrode for a solar cell, comprising (a) a silver powder; (b) a conductive polymer, which is a PEDOT-PSS, Polythiophene, poly(3-alkylthiophene), polypyrrole, poly((2,5-dialkyloxy)-p-phenylene vinyl (Poly((2,5dialkoxy)-p-phenylene vinylene)), poly(p-phenylene vinylene) and poly(p-phenylene) (Poly) P-phenylene)) one or more selected from the group consisting of: (c) a cellulose derivative; and (d) a solvent. Further, the present invention provides a method for forming an electrode of a solar cell using the paste for forming an electrode of the solar cell, a solar cell electrode formed by the above method, and a solar cell including the electrode. EFFECTS OF THE INVENTION The paste for electrode formation of a solar cell obtained by the present invention exhibits the following effects: First, high productivity: formed at the same time as drying at a drying temperature (1 〇〇 to 250 ° (::)) Electrode, so no additional firing steps are required 201117389

第二’高導電率以及優異 電化學性安定 包丨且.隹乾燥溫度（100, 厲以下)下導電性高分子殘存於糊内部， 且平滑地誘導電子流動。 第三，低接觸電阻：顯示低接觸電阻’特別適合非晶 質/晶質異質接面太陽電池。 第四，熱貯藏安定性：與有機黏合劑以及溶劑等之相 溶性優異，熱安定性㈣高，有物理化學狀態變化少的長 處。 第五，高縱橫比：糊的流變特性優異，可以實現高縱 橫比（Aspect ratio)。 I：實施方式;j 用以實施發明之形態 以下’將詳細說明本發明。 依據本發明獲得之太陽電池之電極形成用糊係包含 ⑻銀粉末(silver powder); (b) 導電性高分子，係由pedOT-PSS、聚°塞吩 (Polythiophene)、聚（3-烷基噻吩)(P〇ly(3-alkylthiophene))、 聚。比咯（Polypyrrole)、聚（(2,5二烷氧基）-P-伸苯基伸乙烯 基)(Poly((2,5dialkoxy)-p-phenylene vinylene))、聚(ρ-伸苯基 伸乙稀基）(Poly(p-phenylene vinylene))以及聚（ρ-伸苯 基)(Poly(p-phenylene))組成之族群中選出的1種以上者； (c) 纖維素衍生物；以及 (d)溶劑。 5 201117389 合適的是’依據本發明獲得之電極糊包含(a)銀粉末 (silverpowder)30〜95重量％ ;⑻由PEDOT-PSS、聚D塞吩、 聚（3-烷基噻吩）、聚吼咯、聚（(2,5二烷氧基)-ρ-伸笨基伸乙 烯基）、聚(Ρ-伸苯基伸乙烯基）以及聚(ρ-伸苯基)組成之埃群 中選出1種以上之導電性高分子0.1〜40重量％ ;(c)纖維素中于 生物0.1〜50重量％ ;以及(d)餘量之溶劑。 本發明之「太陽電池之電極形成用電極糊」中包含由 積層構造體構成之單層或多層構成的作為配線板之類的電 路形成用材料所使用之糊。從而，不僅是太陽電池所使用 的電極，其亦適合該等裝置所使用的電配線。 以下，將就各成分作詳細說明。 (a) 銀粉末(silver powder) 本發明之前述銀粉末宜具有0.05至1 Ομπι之平均粒度。 為提高印刷之精密性，應用在太暢電池時大大提高太陽電 池之填充因子(Fill Factor)(以下，稱為「FF」）以提高效率， 宜混合使用具有多種粒子大小之金屬粉末。 前述銀粉末在糊内含有30至95重量％，前述銀含量不 足30重量％時，糊的黏度低'，用印刷絲網印刷法在基材印 刷時會比掩膜之圖案尺寸更寬，有印刷上的問題，另外， 銀含量超過95重量％時，黏度高，導電性粉末難以均勻的 分散，印刷時在掩膜的糊通透性不良而難以形成電極，在 印刷後的基材之表面粗糙度不良。 (b) 導電性高分子 可在本發明中使用的導電性高分子可以使用由 6 201117389 PEDOT-PSS、聚噻吩、聚（3-烷基噻吩）、聚吡洛、聚（(2 5 二炫氧基)_P-伸苯基伸乙烯基）、聚(p-伸笨基伸乙烯基)以及 聚(p-伸苯基）組成之族群中選出的1種以上者。另外，亦可 使用前述導電性高分子中混合溶媒者。特別是由本發明所 使用之PEDOT-PSS、聚噻吩、聚(3_烷基噻吩）、聚吡咯、聚 ((2,5二烷氧基)-P-伸笨基伸乙烯基）、聚(p_伸笨基伸乙烯基） 以及聚(P-伸苯基）組成之族群中選出的i種以上之導電性高 分子與一般的聚苯胺(P〇lyaniUne)之類的導電性高分子相 比，在比電阻、基板附著力、接觸電阻、縱橫比以及黏度 變化率方面顯示顯著差異。 & 前述導電性高分子可以含有〇1至4〇重量％。導電性高 分子之含量不足0.1重量％時，就難以期待導電率之改善效 果’另外’導電性㊉分子含量超過4Q重量％時，因導電性 高分子的低黏度使製造的電極糊形成低黏度，招致印刷後 的圖案線寬之擴散現象，這難以實現高解析度圖案，獲得 優異的縱橫比之電極圖案困難。 (C)纖維素衍生物 用，曰^中前述纖維素衍生物係轉合劑形式發揮作 〃 f性高分子以及溶劑之相溶性優異，會使本發 著電極形成用糊的導電率以及貯藏安定性顯 使用由之前述纖維素衍生物之具雜例，可以 維素紐成域維素^纖維素《及乙基纖 、群中選出的1種以上者。 刖述纖维素衍生物可以含有01至50重量％。前述纖維 201117389 素衍生物之含量不足0.1重量％範圍時，印刷時掩膜之通透 性不良。含量超過30重量％範圍時，在100〜25(TC區域施 行乾燥就會殘存大量的纖維素衍生物，這會作為阻礙電極 糊之硬化率的要素發揮作用，引起基板附著強度下降之問 題。 (d) 溶媒 前述(a)-(c)之成分係在溶媒中混合分散以使用。 此時，可使用的溶媒以沸點在80〜250°C者為佳，具體 例係可以單獨或混合2種以上使用乙酸乙赛路蘇（ethyl cellosolve acetate)、乙酸丁赛路蘇、丙二醇曱醚乙酸酯、丁 基卡必醇乙酸醋（butyl carbitol acetate)、二丙二醇甲喊乙酸 酯、丁基卡必醇、丙二醇單甲醚、二丙二醇單曱醚、丙二 醇單甲謎丙酸醋、乙祕丙酸g旨（ethyl ether propionate)、祐品 醇、十二醇酯（texanol)、乙二醇、丙二醇、二乙二醇、二丙 二醇、乙二醇單曱醚、二乙二醇單甲醚、二乙二醇單***、 三乙二醇、三乙二醇單曱驗、三乙二醇單乙&|、丙二醇單 丁醚、丙二醇曱醚、二丙二醇曱醚、乙二醇單甲醚 '二甲 基胺基曱醛、甲乙酮、γ-丁内酯或者乳酸乙酯等。可以合 適地使用丁基卡必醇乙酸酯、乙二醇或該等之混合物。 前述溶媒可以含有除(a)-(c)之成分外的餘量。 (e) 其他的添加劑 前述以外，依據本發明獲得之電極糊依需要亦可進一 步含有通常糊所含的添加劑。前述添加劑之例可以例舉增 黏劑、安定化劑、分散劑、脫泡劑或界面活性劑等，該等 201117389 成分宜使用0.1〜5重量％。 具有这種組成之本發明的太陽電池之電極形成用糊可 以利用指疋之比率混合前述記載之必要成分與選擇性成 分’且以檀拌機或3轴親等的混煉機將其均勻地分散製得。 合適的是，依據本發明獲得之電極糊係以使用布氏 (Brookfield)HBT黏度系以及#14轉子，以多用途杯在1〇rpm 及25C測定時，具有1至3〇〇pa . S之黏度者為佳。 依據本發明獲得之太陽電池之電極形成用糊沒有額外 的燒成步驟，僅以乾燥步驟就可以形成電極。從而由於不 額外需要燒成步驟，使作業性容易，因低溫乾燥使導電性 高分子殘存於糊内部，有電化學性安定且平滑地誘導電子 流動之長處。特別是應用在非晶質/晶質矽異質接面太陽電 池時其效果更為重大。 本發明另外提供一種太陽電池之電極形成方法，利用 刖述方法製造之太陽電池電極以及包含前述太陽電池電極 的太陽電池，該太陽電池之電極形成方法的特徵為，在基 材之上印刷前述電極糊並乾燥。 本發明之太陽電池之電極形成方法中除了使用前述太 陽電池之電極形成用糊外，基材、印刷以及乾燥當然可以 使用通常太陽電池的製造所使用之方法。作為一例，前述 基材可以為Si基板’前述電極可以為石夕太陽電池之前面電 極’前述印刷可以為絲網印刷’前述乾燥可以在1〇〇〜25〇。〇 進行10分鐘至30分鐘’前述印刷可選擇性調節，以印刷為 20至50μιη之厚度為佳。 201117389 本發明之太陽電池之電極形成方法由於不額外需要燒 成步驟，所以作業性及生產性優異，精密性高，包含利用 依據本發明獲得之電極糊所製造的電極之太陽電池，其效 率高、解析度高，特別適合低溫燒成且量產性優異，應用 在非晶質/晶質矽異質接面太陽電池時有效果更為良好的 長處。 以下，為本發明之理解將提出合適的實施例，不過下 述之實施例只不過為例示本發明者，本發明之範圍並不限 定於下述之實施例。 實施例1至4及比較例1、2 以下述表1記載之成分及含量混合後，用三輥混煉機混 合分散以製成電極糊。 10 201117389 [表] 電極糊(重里 份) 實施例 1 實施例 2 實施例 3 實施例 4 比較例 1 比較例 2 比較例 3 導電性 粉末 銀粉末1 10 30 15 45 10 20 銀粉末2 30 30 65 45 30 80 65 PEDOT- PSS 30 - 10 4 — 聚吡咯 - 10 - 3 - - - 導電性 高分子 聚(Ρ-伸 笨基伸 乙烯基） - 10 - - - - - 聚苯胺 - - - - - - 7 纖維素 羥基 纖維素 4 3 0.5 0.5 5 1 1 衍生物 乙基 纖維素 - 1.5 0.5 0.2 4 2 1 溶媒 丁基卡 必醇乙 酸酯 12.5 7 4 1 25 8 2 乙二醇 12.5 8 4 1 25 8 3 添加劑 脱泡劑 0.5 0.5 0.5 - 0.5 0.5 0.5 分散劑 0.5 - 0.5 0.3 0.5 0.5 0.5 銀粉末1 :平均粒度1.5μιη的球状型銀粉末 銀粉末2 :平均粒度2.5μπΐ的板状型銀粉末 脱泡劑：矽系脱泡劑 分散劑：醇銨鹽 以如下所述的方法對於前述實施例丨至4，以及比較例 1、2中製造的電極糊分別測定其特性（比電阻、基板附著力、 接觸電阻、縱橫比及黏度變化率）。將其結果示於下述表2。 1)比電阻(*ι〇-5ω . cm) 將前述實施例1至4 ’以及比較例i、2中製造的電極糊 分別印刷到基材後’在18〇。(：以15分鐘，2〇〇〇Cj^15八铲 以及220X：以15分鐘硬化後，利用4點探針測定比電^。$ 11 201117389 2) 基板附著力 基於格子附著性評估（ASTMD3359)，印刷在基材上， 再用百格刀（crosscut knife)在硬化後的糊上作100個格子 紋，附以金屬附著力專用膠帶(3M，#610)後撕下，記錄發 生剝離之格子數。 3) 接觸電阻(γπΩ · cm) 以網版印刷技術將前述實施例1至4，以及比較例1、2 中製造的電極糊印刷到太陽電池單元(Cell)之後面，用熱風 式乾燥爐乾燥。然後，在前面印刷線寬ΙΙΟμηι之電極圖案， 再於160。(：乾燥5分鐘。利用燒成爐在22CTC將前述過程中製 造的單元(cell)燒成15分鐘《對這樣處理製成的單元(cell)利 用核心掃描（Correscan)測定接觸電阻。 4) 縱橫比（％) 將線寬ΙΙΟμηι之電極圖案印刷、乾燥、燒成後，用sem 分別測定電極圖案之高度及圖案線寬，求取圖案之高度/圖 案線寬比率並記錄縱橫比（％)。 5) 黏度變化率（％) 將前述實施例1至4，以及比較例1、2中製造的電極糊 在25°C貯藏1個月後’利用布氏(Br00kfield)HBT黏度計t乂 #51轉子在溫度25 C下剪切速率（shear rate)3.84sec-l條件下 測定黏度變化，並觀察黏度變化率。 12 201117389 [表2] 實施例 1 實施例 2 實施例 3 實施例 4 比較例 1 比較例 2 比較例 3 比電胖· (*10·5Ω· cm) 在 180T： 硬化 15分鐘 4.94 6.96 2.39 1.70 32.50 7.16 7.30 在200〇C 硬化 15分鐘 3.61 2.35 1.99 1.19 27.50 5.86 6.02 在220〇C 硬化 15分鐘 1.13 1.57 1.01 0.84 8.79 3.24 4.55 基板 附著力 膠帶附著 力(ASTM D3359) 0 0 0 0 5 10 5 接觸電阻 (mQ*cm) 太陽電池 單元評估 7 7 6 6 9 9 9 縱橫比 (%) 燒成後圖 案高度/ 圖案線寬 比率 21.2 24.7 25 24 13.8 15.5 14.3 黏度 變化率 (%) 25〇C-l 貯藏1個 月後黏度 變化率 2.5 4.7 3.2 3.1 6.9 9.3 5 如前述表2所示，依據本發明之實施例1至4獲得之電極 糊與不含導電性高分子之比較例1 - 2以及含聚苯胺之電極 糊相比，在比電阻、基板附著力、接觸電阻、縱橫比以及 黏度變化率方面顯示了顯著改善之效果，其中本發明包含 由PEDOT-PSS、聚噻吩、聚(3-烷基噻吩）、聚吡咯、聚((2,5 二烷氧基)-P-伸苯基伸乙烯基）、聚(P-伸苯基伸乙烯基）以及 聚(P-伸苯基)組成之族群中選出的1種以上導電性高分子。 其中特別是依據本發明之實施例1至4獲得之電極糊在低溫 燒成時比電阻改善效果較顯著。 【圖式簡辱_說^明】 (無） 【主要元件符號說明】 (無） 13The second 'high conductivity and excellent electrochemical stability are contained. The conductive polymer remains in the paste at a drying temperature (100 or less), and the electron flow is smoothly induced. Third, low contact resistance: shows low contact resistance' is particularly suitable for amorphous/crystalline heterojunction solar cells. Fourth, thermal storage stability: excellent compatibility with organic binders and solvents, high thermal stability (4), and low physicochemical state changes. Fifth, high aspect ratio: The paste has excellent rheological properties and can achieve a high aspect ratio. I: Embodiments; j MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The electrode for forming an electrode for a solar cell obtained according to the present invention comprises (8) a silver powder; (b) a conductive polymer, which is composed of pedOT-PSS, polythiophene, poly(3-alkyl Thiophene (P) (polyalkylphene), poly. Polypyrrole, poly((2,5dialkoxy)-p-phenylene vinylene), poly(ρ-phenylene) One or more selected from the group consisting of poly(p-phenylene vinylene) and poly(p-phenylene); (c) cellulose derivatives; d) Solvent. 5 201117389 It is suitable that the electrode paste obtained according to the invention comprises (a) silver powder (silverpowder) 30 to 95% by weight; (8) by PEDOT-PSS, poly D-cephene, poly(3-alkylthiophene), polyfluorene One of the eucalyptus groups consisting of poly((2,5-dialkyloxy)-ρ-extended vinyl), poly(p-phenylenevinyl), and poly(ρ-phenylene) The above conductive polymer is 0.1 to 40% by weight; (c) 0.1 to 50% by weight of the biomass in the cellulose; and (d) the balance of the solvent. The "electrode paste for forming an electrode for a solar cell" of the present invention includes a paste used as a wiring forming material such as a wiring board which is composed of a single layer or a plurality of layers composed of a laminated structure. Thus, not only the electrodes used in solar cells, but also the electrical wiring used in such devices. Hereinafter, each component will be described in detail. (a) Silver powder The aforementioned silver powder of the present invention preferably has an average particle size of from 0.05 to 1 μm. In order to improve the precision of printing, the solar cell's Fill Factor (hereinafter referred to as "FF") is used to increase the efficiency of the battery, and it is preferable to use a metal powder having a plurality of particle sizes. The silver powder contains 30 to 95% by weight in the paste, and when the silver content is less than 30% by weight, the viscosity of the paste is low, and the printing screen printing method is wider than the mask pattern when printing on the substrate. In addition, when the content of silver exceeds 95% by weight, the viscosity is high, and it is difficult to uniformly disperse the conductive powder, and the paste permeability in the mask is poor during printing, and it is difficult to form an electrode on the surface of the substrate after printing. Poor roughness. (b) Conductive polymer The conductive polymer which can be used in the present invention can be used by 6 201117389 PEDOT-PSS, polythiophene, poly(3-alkylthiophene), polypyrrole, poly((2 5 One or more selected from the group consisting of oxy)_P-phenylene vinyl), poly(p-extended vinyl), and poly(p-phenylene). Further, those in which the above-mentioned conductive polymer is mixed with a solvent can also be used. In particular, PEDOT-PSS, polythiophene, poly(3-alkylthiophene), polypyrrole, poly((2,5-dialkyloxy)-P-extended base-extended vinyl), poly(p) used in the present invention More than one type of conductive polymer selected from the group consisting of a group of styrene-based vinyl groups and poly(P-phenylene) is compared with a conductive polymer such as general polyaniline (P〇lyaniUne). Significant differences were shown in specific resistance, substrate adhesion, contact resistance, aspect ratio, and viscosity change rate. & The conductive polymer may contain 〇1 to 4% by weight. When the content of the conductive polymer is less than 0.1% by weight, it is difficult to expect an effect of improving the conductivity. When the content of the conductivity is more than 4% by weight, the electrode paste formed has a low viscosity due to the low viscosity of the conductive polymer. This leads to a diffusion phenomenon of the pattern line width after printing, which makes it difficult to realize a high-resolution pattern, and it is difficult to obtain an electrode pattern having an excellent aspect ratio. (C) For the cellulose derivative, the cellulose derivative-based conversion agent is excellent in compatibility with a solvent and a solvent, and the conductivity and storage stability of the electrode-forming paste are obtained. It is possible to use one of the above-mentioned cellulose derivatives, and it is possible to use one or more selected from the group of vitamins and celluloses. The cellulose derivative may be contained in an amount of from 01 to 50% by weight. When the content of the above-mentioned fiber 201117389 derivative is less than 0.1% by weight, the permeability of the mask at the time of printing is poor. When the content is in the range of more than 30% by weight, a large amount of cellulose derivative remains in the range of 100 to 25 (the TC region is dried, which acts as an element which inhibits the hardening rate of the electrode paste, and causes a problem that the substrate adhesion strength is lowered. The components (a) to (c) of the solvent are mixed and dispersed in a solvent to be used. In this case, the solvent to be used is preferably a boiling point of 80 to 250 ° C, and specific examples may be used alone or in combination of two or more. Use ethyl cellosolve acetate, butyl sulphate acetate, propylene glycol oxime ether acetate, butyl carbitol acetate, dipropylene glycol methyl acetate, butyl carbene Alcohol, propylene glycol monomethyl ether, dipropylene glycol monoterpene ether, propylene glycol monomethyl propyl vinegar, ethyl ether propionate, estradiol, texanol, ethylene glycol, propylene glycol , diethylene glycol, dipropylene glycol, ethylene glycol monoterpene ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol single test, triethylene glycol single B &|, propylene glycol monobutyl ether, propylene glycol oxime ether, dipropylene Glycol oxime ether, ethylene glycol monomethyl ether 'dimethylamino valeraldehyde, methyl ethyl ketone, γ-butyrolactone or ethyl lactate, etc. butyl carbitol acetate, ethylene glycol or The above solvent may contain the balance other than the components (a) to (c). (e) Other additives The electrode paste obtained according to the present invention may further contain a general paste as needed. The additive may be exemplified by a tackifier, a stabilizer, a dispersant, a defoaming agent or a surfactant, and the components of the 201117389 are preferably used in an amount of 0.1 to 5% by weight. The electrode for forming an electrode for a solar cell can be obtained by mixing the essential components and the selective component described above with a ratio of the finger 且 and uniformly dispersing it by a kneading machine or a three-axis kneading machine. Suitably, The electrode paste obtained by the present invention is preferably a Brookfield HBT viscosity system and a #14 rotor, and has a viscosity of 1 to 3 Å Pa. S when measured in a multipurpose cup at 1 rpm and 25 C. Solar battery power obtained according to the present invention The electrode forming paste has no additional baking step, and the electrode can be formed only by the drying step. Therefore, since the baking step is not additionally required, workability is easy, and the conductive polymer remains in the paste due to low-temperature drying, and there is electrochemical It is stable and smooth to induce the advantages of electron flow. Especially when applied to amorphous/crystalline 矽 heterojunction solar cells, the effect is more important. The present invention further provides a method for forming an electrode of a solar cell, which utilizes a method of description A solar cell electrode produced and a solar cell including the solar cell electrode, wherein the electrode forming method of the solar cell is characterized in that the electrode paste is printed on a substrate and dried. In the electrode forming method of the solar cell of the present invention, in addition to the paste for electrode formation of the solar cell, the substrate, printing, and drying can of course be carried out by a method generally used for the production of a solar cell. As an example, the substrate may be a Si substrate. The electrode may be a front surface electrode of a stone solar cell. The printing may be screen printing. The drying may be 1 to 25 Å.进行 10 minutes to 30 minutes' The printing described above can be selectively adjusted to a thickness of 20 to 50 μm. 201117389 The method for forming an electrode for a solar cell according to the present invention is excellent in workability and productivity, and has high precision, and the solar cell including the electrode made of the electrode paste obtained by the present invention is high in efficiency. It has high resolution and is especially suitable for low-temperature firing and excellent mass productivity. It is more effective when applied to amorphous/crystalline 矽 heterojunction solar cells. In the following, a suitable embodiment will be set forth for the understanding of the present invention, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the embodiments described below. Examples 1 to 4 and Comparative Examples 1 and 2 were mixed with the components and contents described in Table 1 below, and then mixed and dispersed in a three-roll kneader to prepare an electrode paste. 10 201117389 [Table] Electrode paste (heavy portion) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Conductive powder Silver powder 1 10 30 15 45 10 20 Silver powder 2 30 30 65 45 30 80 65 PEDOT- PSS 30 - 10 4 — Polypyrrole - 10 - 3 - - - Conductive polymer poly(Ρ-steep base vinyl) - 10 - - - - - Polyaniline - - - - - - 7 Cellulose hydroxycellulose 4 3 0.5 0.5 5 1 1 Derivative ethylcellulose - 1.5 0.5 0.2 4 2 1 Solvent butyl carbitol acetate 12.5 7 4 1 25 8 2 Glycol 12.5 8 4 1 25 8 3 Additive defoamer 0.5 0.5 0.5 - 0.5 0.5 0.5 Dispersant 0.5 - 0.5 0.3 0.5 0.5 0.5 Silver powder 1: Spherical silver powder silver powder with an average particle size of 1.5 μηη 2: Plate-like silver powder with an average particle size of 2.5 μπΐ Foaming agent: oxime defoaming agent dispersing agent: alcohol ammonium salt The characteristics of the electrode paste prepared in the above Examples 丨 to 4 and Comparative Examples 1 and 2 were measured by the following methods (specific resistance, substrate adhesion) , contact resistance, aspect ratio and viscosity change rate). The results are shown in Table 2 below. 1) Specific resistance (*ι〇-5ω.cm) The electrode pastes produced in the above Examples 1 to 4' and Comparative Examples i and 2 were printed on a substrate, respectively, at 18 Å. (: 15 minutes, 2 〇〇〇 Cj^15 eight shovel and 220X: After hardening for 15 minutes, the specific electric power was measured using a 4-point probe. $11 201117389 2) Substrate adhesion based on lattice adhesion evaluation (ASTMD3359) Printed on the substrate, and then use a crosscut knife to make 100 plaid patterns on the hardened paste, and then peel off with special metal adhesion tape (3M, #610), and record the stripped strip. number. 3) Contact resistance (γπΩ · cm) The electrode pastes prepared in the foregoing Examples 1 to 4 and Comparative Examples 1 and 2 were printed on the surface of the solar cell unit (Cell) by screen printing technique, and dried by a hot air drying oven. . Then, the electrode pattern of the line width ΙΙΟμηι is printed on the front side, and then at 160. (: Drying for 5 minutes. The cell manufactured in the foregoing process was fired at 22 CTC for 15 minutes in a firing furnace. "The contact resistance was measured by a core scan (Correscan) for the cell thus processed. 4) Ratio (%) After the electrode pattern of the line width ΙΙΟμηι was printed, dried, and fired, the height of the electrode pattern and the line width of the pattern were measured by sem, and the height of the pattern/pattern line width ratio was calculated and the aspect ratio (%) was recorded. 5) Viscosity change rate (%) After the electrode pastes prepared in the above Examples 1 to 4 and Comparative Examples 1 and 2 were stored at 25 ° C for 1 month, 'Using a Brookfield (Br00kfield) HBT viscometer t乂#51 The viscosity of the rotor was measured at a shear rate of 3.84 sec-l at a temperature of 25 C, and the rate of change of viscosity was observed. 12 201117389 [Table 2] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Specific fat (*10·5 Ω·cm) at 180T: Hardened for 15 minutes 4.94 6.96 2.39 1.70 32.50 7.16 7.30 Hardening at 200 °C for 15 minutes 3.61 2.35 1.99 1.19 27.50 5.86 6.02 Hardening at 220 °C for 15 minutes 1.13 1.57 1.01 0.84 8.79 3.24 4.55 Substrate adhesion Tape adhesion (ASTM D3359) 0 0 0 0 5 10 5 Contact resistance ( mQ*cm) Solar cell evaluation 7 7 6 6 9 9 9 Aspect ratio (%) Pattern height after firing / Pattern line width ratio 21.2 24.7 25 24 13.8 15.5 14.3 Viscosity change rate (%) 25〇Cl Storage for 1 month Post-viscosity change rate 2.5 4.7 3.2 3.1 6.9 9.3 5 As shown in Table 2 above, the electrode paste obtained according to Examples 1 to 4 of the present invention and Comparative Example 1-2 containing no conductive polymer and the electrode containing polyaniline The paste exhibits a significant improvement in specific resistance, substrate adhesion, contact resistance, aspect ratio, and viscosity change rate, wherein the present invention comprises PEDOT-PSS, polythiophene, poly(3-alkylthiophene), Polypyrrole, poly ((2,5 Alkoxy) -P- stretch vinyl phenylene), poly (vinyl extending the P-phenylene) and poly (the P-phenylene) selected from the group consisting of one or more kinds of conductive polymer. Among them, in particular, the electrode paste obtained according to Examples 1 to 4 of the present invention has a remarkable effect of improving electric resistance at the time of low-temperature firing. [Illustration of the form humiliation _ say ^ Ming] (none) [Main component symbol description] (none) 13

Claims (1)

201117389 七、申請專利範圍： 1. 一種太陽電池之電極形成用糊，其包含 (a) 銀粉末； (b) 導電性高分子（conducting polymer)，係由 PEDOT-PSS、聚噻吩、聚(3_烷基噻吩）、聚吡咯、聚((2,5 二院氧基)-p-伸苯基伸乙烯基(phenylene vinylene))、聚 (p-伸苯基伸乙烯基）以及聚(p-伸苯基）組成之族群中選 出的1種以上者； (c) 纖維素衍生物；以及 (d) 溶劑。 2. 如申請專利範圍第1項記載的太陽電池之電極形成用 糊，其包含 ⑻銀粉末30至95重量％ ; (b) 導電性高分子0.1至40重量％ ; (c) 纖維素衍生物0.1至50重量％ ;以及 (d) 餘量之溶劑。 3. 如申請專利範圍第1項記載的太陽電池之電極形成用 糊，其中前述導電性高分子係由PEDOT-PSS、聚噻吩、 聚(3-烷基噻吩）、聚。比咯、聚((2,5二烷氧基)-P-伸苯基伸 乙烯基）、聚(P-伸苯基伸乙烯基）以及聚(P-伸苯基）組成 之族群中選出的1種以上者。 4. 如申請專利範圍第1項記載的太陽電池之電極形成用 糊，其中前述纖維素衍生物係由羥基纖維素、甲基纖維 素、硝化纖維素以及乙基纖維素組成之族群中選出的1 14 201117389 種以上者。 申月專利範圍第1項記載的太陽電池之電極形成用 糊，其中前述溶劑之沸點在80〜250。(：。 申明專利範圍第1項記載的太陽電池之電極形成用 糊，其t前述太陽電池係非晶質/晶質的石夕異質接面太 %電池。 7. -種太陽電池之電極形成方法，其舰為，在基材之上 印刷從中請專利範圍第1至6項選出之任-項的糊並乾 燥。 8. —種太陽電池電極’係依據申請專利範圍第7項製造者。 9·如申請專利範圍第8項記載的太陽電池電極，其中前述 太陽電池係非晶質/晶質的矽異質接面太陽電池。 1〇·—種太陽電池，包含申請專利範圍第8項記載的太陽電 池電極。 15 201117389 四、指定代表圖： (一) 本案指定代表圖為：第（ ）圖。（無) (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201117389 VII. Patent application scope: 1. A paste for forming an electrode for a solar cell, comprising (a) a silver powder; (b) a conducting polymer, which is composed of PEDOT-PSS, polythiophene, poly(3) _Alkylthiophene), polypyrrole, poly((2,5 oxarene vinyl)-p-phenylene vinylene), poly(p-phenylenevinyl), and poly(p-stretch) One or more selected from the group consisting of phenyl); (c) a cellulose derivative; and (d) a solvent. 2. The electrode for forming an electrode for a solar cell according to claim 1, which comprises (8) silver powder 30 to 95% by weight; (b) conductive polymer 0.1 to 40% by weight; (c) cellulose derivative 0.1 to 50% by weight; and (d) the balance of the solvent. 3. The paste for electrode formation of a solar cell according to claim 1, wherein the conductive polymer is PEDOT-PSS, polythiophene, poly(3-alkylthiophene), or poly. 1 selected from the group consisting of pyrrole, poly((2,5-dialkyloxy)-P-phenylenevinyl), poly(P-phenylenevinyl), and poly(P-phenylene) More than one. 4. The electrode for forming an electrode for a solar cell according to claim 1, wherein the cellulose derivative is selected from the group consisting of hydroxycellulose, methylcellulose, nitrocellulose, and ethylcellulose. 1 14 201117389 More than one species. The electrode for forming an electrode for a solar cell according to the first aspect of the invention, wherein the solvent has a boiling point of 80 to 250. (A. The paste for forming an electrode for a solar cell according to the first aspect of the invention, wherein the solar cell is amorphous or crystalline, and the heterojunction of the solar cell is too%. 7. The electrode formation of the solar cell In the method, the ship is printed on the substrate, and the paste selected from items 1 to 6 of the patent scope is printed and dried. 8. The solar cell electrode is manufactured according to the seventh item of the patent application. 9. The solar cell electrode according to claim 8, wherein the solar cell is an amorphous/crystalline heterogeneous junction solar cell. 1〇·-type solar cell includes the eighth item of the patent application scope. Solar cell electrodes 15 201117389 IV. Designation of representative drawings: (1) The representative representative of the case is: ( ) (None) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, Please reveal the chemical formula that best shows the characteristics of the invention:
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